JP3859906B2 - Resin composition for inkjet recording material and inkjet recording material - Google Patents

Description

（式中、Ｒ^２は炭素数２〜８のアルキレン基を表し、Ｒ^３は炭素数１〜４のアルキル基を表し、Ｒ^４およびＲ^５はそれぞれ独立して炭素数１〜１２のアルキル基、炭素数１〜１２のアリールアルキル基または炭素数１〜１２の脂環式アルキル基を表し、Ｘ⁻はハロゲンイオン、ＣＨ_３ＯＳＯ_３ ⁻またはＣ_２Ｈ_５ＯＳＯ_３ ⁻を表す）
【０００７】
また、前記カチオン性高分子化合物は下記一般式（１）で表されるエチレン性構造単位が６５モル％〜９９モル％、下記一般式（２）で表されるアクリレート構造単位が１５モル％以下、および下記一般式（４）で表されるアクリルアミド構造単位が１モル％〜３５モル％からなる、不規則に配列した重量平均分子量が１，０００〜５０，０００の線状のカチオン性高分子化合物であることができる。
【化４】

（式中、Ｒ^２は炭素数２〜８のアルキレン基、Ｒ^３は炭素数１〜４のアルキル基、Ｒ^４は炭素数１〜１２のアルキル基、炭素数１〜１２のアリールアルキル基または炭素数１〜１２の脂環式アルキル基を表し、Ｘ⁻はハロゲンイオン、ＣＨ_３ＯＳＯ_３ ⁻またはＣ_２Ｈ_５ＯＳＯ_３ ⁻を示す）
【０００８】
また、前記押出グレードのポリビニルアルコールと前記カチオン性高分子化合物との重量比は６０／４０〜８５／１５の範囲内であることができる。本発明のインクジェット記録材は、基材上に積層されたインク受容層を有するインクジェット記録材であって、前記インク受容層が上記インクジェット記録材用樹脂組成物のいずれかを主成分として有することを特徴とする。
【０００９】
【発明を実施するための好ましい形態】
本発明のインクジェット記録材は、基材上にインク受容層を有する。インク受容層は、以下に示すように押出グレードのＰＶＡに特定のカチオン性高分子化合物を含む樹脂組成物を用いて形成される。特定のカチオン性高分子化合物を配合することにより、インク受容層の耐湿性を向上させることができる。かかるカチオン性高分子化合物は、水不溶性であり、ポリマーに対してある程度の親和性があり、樹脂表面にブリードアウトしないものが好ましい。本発明に好ましく用いられるカチオン性高分子化合物を以下に示す。
【００１０】
下記一般式（１）で表されるエチレン構造単位が６５モル％〜９９モル％、下記一般式（２）で表されるアクリレート構造単位が１５モル％以下、および下記一般式（３）で表されるアクリルアミド構造単位が１モル％〜３５モル％からなる、不規則に配列した重量平均分子量が１，０００〜５０，０００の線状のカチオン性高分子化合物は、本発明に好ましく用いられる。
【化５】

（式中、Ｒ^２は炭素数２〜８のアルキレン基を表し、Ｒ^３は炭素数１〜４のアルキル基を表し、Ｒ^４およびＲ^５はそれぞれ独立して炭素数１〜１２のアルキル基、炭素数１〜１２のアリールアルキル基または炭素数１〜１２の脂環式アルキル基を表し、Ｘ⁻はハロゲンイオン、ＣＨ_３ＯＳＯ_３ ⁻またはＣ_２Ｈ_５ＯＳＯ_３ ⁻を表す）
【００１１】
本発明においては、上記一般式（３）で表されるアクリルアミド構造単位の代わりに下記一般式（４）で表されるアクリルアミド構造単位を含む、線状に不規則に配列した、重量平均分子量が１，０００〜５０，０００のカチオン性高分子化合物を好ましく用いることができる。
【化６】

（式中、Ｒ^２は炭素数２〜８のアルキレン基、Ｒ^３は炭素数１〜４のアルキル基、Ｒ^４は炭素数１〜１２のアルキル基、炭素数１〜１２のアリールアルキル基または炭素数１〜１２の脂環式アルキル基を表し、Ｘ⁻はハロゲンイオン、ＣＨ_３ＯＳＯ_３ ⁻またはＣ_２Ｈ_５ＯＳＯ_３ ⁻を示す）
【００１２】
本発明において、ポリビニルアルコール（ＰＶＡ）とカチオン性高分子化合物との重量比は６０／４０〜８５／１５の範囲内であることが特に好ましい。カチオン性高分子化合物が１５重量部以上であれば、得られるインクジェット記録材を高温、高湿度下で保存しても印字のにじみの状態は良好であった。カチオン性高分子化合物が４０重量部以内であれば、得られるインクジェット記録材の印字品質は優れたものであった。ただし、カチオン性高分子化合物が５０重量部を越すとＰＶＡに対してカチオン性高分子化合物の分散不良を生じ、得られるインクジェット記録材のインク受容層に粒子状のブツが生じることがあるので、分散状態に注意が必要となる。
【００１３】
本発明のインクジェット記録材用樹脂組成物は、ＰＶＡおよびカチオン性高分子化合物の他に、さらにカチオン性活性剤またはノニオン性活性剤を含めることができる。本発明において、カチオン性活性剤またはノニオン性活性剤の樹脂中の含有量は１重量％〜１０重量％の範囲内であることが好ましい。
本発明に好ましく用いられるカチオン性活性剤としては、ポリエチレンイミン、第４級アンモニウムクロライド、第４級アンモニウムサルフェート等が挙げられ、本発明に好ましく用いられるノニオン性活性剤としては、ポリオキシエチレンアルキルアミン、グリセリン脂肪酸エステル等が挙げられる。
【００１４】
本発明において、インク受容層の形成に用いられるＰＶＡは冷水可溶タイプのＰＶＡであり、ケン化度が約２０〜９０％であることが好ましく、分解温度と融点（成形温度）との差が２０℃以上であることが好ましい。
分解温度と融点との温度差を２０℃以上にするためには、例えば、ＰＶＡの粘度平均重合度を２００〜１０００に調整することにより、またはＰＶＡとエチレン性モノマーとの共重合体を形成することにより、またはＰＶＡに可塑剤を添加することにより、温度差を２０℃以上にすることができる。ＰＶＡとエチレン性モノマーとの共重合体を形成することにより温度差を設定する場合には、例えば、Ｎ−ビニルピロリドンを１０モル％程度重合するとよい。可塑剤を添加することにより温度差を設定する場合には、グリセリン、エチレングリコール等を１５重量％程度添加することが好ましい。このようにして、ＰＶＡの融点を１８０℃以下にすることができ、したがって分解温度と融点との温度差を２０℃以上にすることができる。
【００１５】
さらに、本発明に用いられるＰＶＡはネッキング（押出機から押し出されたフィルムまたはシートが横方向に収縮してたわむこと）を改良するために、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）が２．８以上であることが好ましい。
【００１６】
本発明の樹脂組成物には、インクジェット記録材の手触りや柔らかさ等、材料の風合いを改良するため可塑剤等を含めることができる。本発明に好ましく用いられる可塑剤としては、ポリエチレングリコール（ＰＥＧ）等が挙げられる。また、ブロッキングを防止するために充填剤を含めることができる。本発明に好ましく用いられる充填剤としては例えばタルク等の無機充填材を挙げることができる。
【００１７】
本発明の樹脂組成物を用いてインクジェット記録材のインク受容層を形成するには、樹脂を配合した後、二軸押出機を用いて、好ましくは同方向二軸押出機を用いて混合してから、ペレット化しておくことが好ましい。なお、ペレット化は約１６０℃の温度で行うことが好ましい。
本発明のインクジェット記録材を用いて、通常のインクジェット法により画像記録を行うことができ、良好な画像を得ることができる。
【００１８】
【実施例】
以下に本発明を実施例を用いて具体的に説明するが、本発明はこれらに限定されるものではない。
実施例１
一般式（１）で表されるエチレン構造単位が６５モル％、一般式（２）で表されるアクリレート構造単位が５モル％、および一般式（３）で表されるアクリルアミド構造単位が３０モル％からなるカチオン性高分子化合物を用意した。ただし、カチオン性高分子化合物は、一般式（２）で表されるアクリレート構造単位のＲ^１がＣ_２Ｈ_５であり、一般式（３）で表されるアクリルアミド構造単位のＲ^２がエチレン基、Ｒ^３、Ｒ^４およびＲ^５がそれぞれメチル基、Ｘ⁻がＣ_２Ｈ_５ＯＳＯ_３ ⁻のカチオン性高分子化合物である。また、カチオン性高分子化合物の重量平均分子量は２３，０００であった。なお、カチオン性高分子化合物における各構造単位のモル分率はＮＭＲ測定により求めた。
【００１９】
次いで、ＰＶＡ（（株）クラレ製、商品名「ＣＰ−１０００」）７０重量％と、用意したカチオン性高分子化合物３０重量％とを二軸押出機に投入して１６０℃の温度で混合し、ペレット化し、次いで二軸押出機を用いて１９０℃の条件で溶融押し出しを行ない、厚さ４０μｍのフィルムを作成した。その後、得られたフィルムと厚さ１００μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムとを重ね合わせて１９０℃の温度でラミネートし、本発明のインクジェット記録材を得た。
【００２０】
実施例２
実施例１において、二軸押出機に投入するＰＶＡとカチオン性高分子化合物との割合を５０重量％／５０重量％に変更した以外は実施例１と同様にしてインクジェット記録材を作製した。
【００２１】
実施例３
実施例２において、二軸押出機に投入するＰＶＡとカチオン性高分子化合物との割合を９５重量％／５重量％に変更した以外は実施例１と同様にしてインクジェット記録材を作製した。
【００２２】
比較例１
ＰＶＡ（（株）クラレ製、商品名「ＣＰ−１０００」）を押出機により１９０℃の条件下、溶融押し出しを行なって、厚さ４０μｍのフィルムを作成した。次いで、得られたフィルムと厚さ１００μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムとを１９０℃の温度でラミネートして、比較用のインクジェット記録材を得た。
【００２３】
得られた実施例１〜３，および比較例１のインクジェット記録材について、以下に示す評価方法に従い、印字品質（画像品質）、インクにじみ等の耐湿性の評価を行った。
評価方法
１） 印字出力品質の評価
実施例１および比較例１のインクジェット記録材（サンプル）それぞれに、ヒュ−レットパッカード社製、商品名「デザインジェット ３５０Ｃ」を用いて、独自に作製した印字パターンを印刷した。印刷された印字パターンを肉眼で観察して、印字品質の評価を行なった。ただし、評価基準は以下の通りである。
評価基準：
Ａ 優れている
Ｂ レベル「Ａ」には達しないが実用レベルの範囲内である
Ｃ 劣る
【００２４】
２） 耐湿性の評価
印字出力品質の評価で用いたインクジェット記録材（サンプル）を温度４０℃、相対湿度９０％ＲＨに設定した恒温恒湿槽内に入れて２４時間放置し、印字パターンの線のにじみについて評価を行った。ただし、線のにじみは下記式により、線のにじみ率で示した。にじみ率が１１０％を越すと、実用的でなくなる。
【数１】

ただし、試験後とはサンプルを恒温恒湿槽に入れて２４時間放置した後をいい、試験前とはサンプルを恒温恒湿槽に入れる前をいう。
得られた結果を表１に示す。
【００２５】
表１の結果から明らかなように、本発明に係る特定のカチオン性高分子化合物を含有する樹脂組成物を用いて形成した記録材は、印字品質が優れており、かつインクのにじみの状態が良好で、耐湿性に優れていた。
特に、ＰＶＡとカチオン性高分子化合物との重量比が６０／４０〜８５／１５の範囲内にある実施例１は印字品質の評価および線のにじみ率の評価ともに優れた結果が得られた。なお、使用したＰＶＡの商品名「ＣＰ−１０００」の分解温度は２００℃、融点は１７４℃であり、その温度差は２６℃であった。ただし、分解（開始）温度はＪＩＳ−Ｋ−７１２０に準じて測定した開始温度を分解温度とし、融点はＪＩＳ−Ｋ−００６４に準じて測定した値を融点とした。
なお、得られたインク受容層にはブツの発生が見られなかった。
【００２６】
実施例４
重合度が３００，Ｍｗ／Ｍｎ＝２．７のポリ酢酸ビニル３０部と、重合度が１７００，Ｍｗ／Ｍｎ＝２．７のポリ酢酸ビニル２０部とを、メタノール溶液で混合し、アルカリ触媒下で酢酸ビニル部分の６０モル％をけん化した後、乾燥し、重合度が６００，Ｍｗ／Ｍｎ＝３．６のＰＶＡ（Ｉ）を製造した。製造されたＰＶＡ（Ｉ）の分解温度と融点との温度差は２７℃であった。
【００２７】
実施例１において、ＰＶＡとして商品名「ＣＰ−１０００」の代わりに製造されたＰＶＡ（Ｉ）を使用した以外は実施例１と同様にしてインクジェット記録材を作成した。ただし、ＰＶＡ（Ｉ）およびカチオン性高分子化合物を二軸押出機に投入して、溶融押し出しを行い、厚さ４０μｍのフィルムを作製する際の押し出しは良好であった。
【００２８】
実施例５
４モル％のＮ−ビニルピロリドンを共重合したポリ酢酸ビニルにアルカリ触媒下で酢酸ビニル部分の８２モル％をけん化した後、乾燥し、重合度が５００，Ｍｗ／Ｍｎ＝２．７のＰＶＡ（II）を調成した。また、４モル％のＮ−ビニルピロリドンを共重合したポリ酢酸ビニルにアルカリ触媒下で酢酸ビニル部分をけん化した後、乾燥し、重合度が１７００，Ｍｗ／Ｍｎ＝２．７のＰＶＡ（III）を調成した。ＰＶＡ（II）１００部とＰＶＡ（III）２０部とを混合して重合し、重合度が９４０，Ｍｗ／Ｍｎ＝３．１，けん化度が８３モル％のＰＶＡ（IV）を製造した。製造されたＰＶＡ（IV）の分解温度と融点との温度差は２４℃であった。
【００２９】
実施例１において、ＰＶＡとして商品名「ＣＰ−１０００」の代わりに製造されたＰＶＡ（IV）を使用した以外は実施例１と同様にしてインクジェット機録材を作製した。ただし、ＰＶＡ（IV）およびカチオン性高分子化合物を二軸押出機に投入して溶融押し出しを行い、厚さ４０μｍのフィルムを作製する際の押し出しは良好であった。
【００３０】
実施例４および実施例５で得られたインクジェット記録材について、実施例１と同様に「印字出力品質の評価」および「耐湿性の評価」を行った。その結果を表１に示す。表１から明らかなように、「印字品質の評価」は共にレベル「Ａ」の評価であり、「線のにじみ率」は共に１００％で、良好な耐湿性を示した。
【００３１】
【表１】

【００３２】
【発明の効果】
以上詳しく説明したように、本発明のインクジェット記録材用樹脂を用いて作製したインクジェット記録材はインク受容層内にカチオン性物質が分散されているので、印字品質に優れ、かつ、高温多湿下で保存されてもインクの滲み状態も良好で耐湿性に優れたものであった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a resin composition for an ink jet recording material, an ink jet recording material, and a method for producing the same, and particularly to an ink jet recording material suitable for performing recording by an ink jet method using an aqueous ink, and the ink jet recording material. The present invention relates to a suitable resin composition and a method for producing the same.
[0002]
[Prior art]
Recording by the ink jet method has no noise, enables high-speed printing, and is low in cost. Therefore, it is used in image information output devices such as color copies and computers, and is rapidly spreading. As the conventional ink jet recording material, many ink jet recording materials are known in which a hydrophilic resin such as polyvinyl alcohol (PVA) or polyvinyl pyrrolidone is coated on a base material to form an ink receiving layer. In order to apply a coating liquid made of a hydrophilic resin onto a substrate, many coating methods such as casting are used.
[0003]
However, when the ink receiving layer is formed by the coating method, the thickness of the ink receiving layer is reduced, so that the ink absorption capability is low, and problems such as image unevenness and a decrease in the drying speed occur. In addition, a method of providing an ink receiving layer by a melt extrusion method using a thermoplastic PVA resin has also been studied, but many of the extrusion grade PVA used in the melt extrusion method have low water resistance, such as ink bleeding. There was a problem with image storage stability.
[0004]
[Problems to be solved by the invention]
The present invention has been made to solve the above-mentioned problems. The object of the present invention is to form an ink-receiving layer of an ink jet recording material by an extrusion-grade PVA using an extrusion grade PVA, or to spread ink. It is to provide an ink jet recording material excellent in moisture resistance and a method for producing the same, and to provide a resin composition for an ink jet recording material used for the ink jet recording material.
[0005]
[Means for Solving the Problems]
The resin composition for an ink jet recording material of the present invention is characterized by comprising an extrusion grade polyvinyl alcohol as a main component and a cationic polymer compound.
[0006]
Here, in the cationic polymer compound, the ethylene structural unit represented by the following general formula (1) is 65 mol% to 99 mol%, and the acrylate structural unit represented by the following general formula (2) is 15 mol% or less. And a linear cationic polymer having an irregularly arranged weight average molecular weight of 1,000 to 50,000, wherein the acrylamide structural unit represented by the following general formula (3) is 1 mol% to 35 mol% It can be a compound.
[Chemical 3]

Wherein R ² represents an alkylene group having 2 to 8 carbon atoms, R ³ represents an alkyl group having 1 to 4 carbon atoms, and R ⁴ and R ⁵ are each independently an alkyl group having 1 to 12 carbon atoms. represents an alicyclic alkyl group having 1 to 12 arylalkyl group or a carbon number of 1 to 12 carbon atoms, X ^- is a halogen _ion, CH 3 OSO ₃ ^- represents a) ^- or _C 2 _H 5 OSO ₃
[0007]
The cationic polymer compound has an ethylenic structural unit represented by the following general formula (1) of 65 mol% to 99 mol% and an acrylate structural unit represented by the following general formula (2) of 15 mol% or less. And a linear cationic polymer having an irregularly arranged weight average molecular weight of 1,000 to 50,000, wherein the acrylamide structural unit represented by the following general formula (4) is 1 mol% to 35 mol% It can be a compound.
[Formula 4]

(Wherein R ² is an alkylene group having 2 to 8 carbon atoms, R ³ is an alkyl group having 1 to ⁴ carbon atoms, R ⁴ is an alkyl group having 1 to 12 carbon atoms, an arylalkyl group having 1 to 12 carbon atoms, or represents an alicyclic alkyl group having 1 to 12 carbon atoms, X ^- is a halogen _ion, CH 3 OSO ₃ ^- shows a) ^- or _C 2 _H 5 OSO ₃
[0008]
The weight ratio of the extrusion grade polyvinyl alcohol to the cationic polymer compound may be in the range of 60/40 to 85/15. The ink jet recording material of the present invention is an ink jet recording material having an ink receiving layer laminated on a substrate, wherein the ink receiving layer has any one of the resin compositions for ink jet recording materials as a main component. Features.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
The ink jet recording material of the present invention has an ink receiving layer on a substrate. The ink receiving layer is formed using a resin composition containing a specific cationic polymer compound in extrusion grade PVA as shown below. By blending a specific cationic polymer compound, the moisture resistance of the ink receiving layer can be improved. Such a cationic polymer compound is preferably water-insoluble, has a certain degree of affinity for the polymer, and does not bleed out on the resin surface. Cationic polymer compounds preferably used in the present invention are shown below.
[0010]
The ethylene structural unit represented by the following general formula (1) is 65 mol% to 99 mol%, the acrylate structural unit represented by the following general formula (2) is 15 mol% or less, and the following general formula (3) An irregularly arranged linear cationic polymer compound having a weight average molecular weight of 1,000 to 50,000 and comprising 1 mol% to 35 mol% of acrylamide structural units is preferably used in the present invention.
[Chemical formula 5]

Wherein R ² represents an alkylene group having 2 to 8 carbon atoms, R ³ represents an alkyl group having 1 to 4 carbon atoms, and R ⁴ and R ⁵ are each independently an alkyl group having 1 to 12 carbon atoms. represents an alicyclic alkyl group having 1 to 12 arylalkyl group or a carbon number of 1 to 12 carbon atoms, X ^- is a halogen _ion, CH 3 OSO ₃ ^- represents a) ^- or _C 2 _H 5 OSO ₃
[0011]
In the present invention, the acrylamide structural unit represented by the following general formula (4) is used instead of the acrylamide structural unit represented by the general formula (3), and the weight average molecular weight is irregularly arranged linearly. 1,000 to 50,000 cationic polymer compounds can be preferably used.
[Chemical 6]

(Wherein R ² is an alkylene group having 2 to 8 carbon atoms, R ³ is an alkyl group having 1 to ⁴ carbon atoms, R ⁴ is an alkyl group having 1 to 12 carbon atoms, an arylalkyl group having 1 to 12 carbon atoms, or represents an alicyclic alkyl group having 1 to 12 carbon atoms, X ^- is a halogen _ion, CH 3 OSO ₃ ^- shows a) ^- or _C 2 _H 5 OSO ₃
[0012]
In the present invention, the weight ratio of polyvinyl alcohol (PVA) to the cationic polymer compound is particularly preferably in the range of 60/40 to 85/15. When the amount of the cationic polymer compound was 15 parts by weight or more, even if the obtained inkjet recording material was stored under high temperature and high humidity, the bleeding state of printing was good. When the cationic polymer compound was within 40 parts by weight, the print quality of the obtained inkjet recording material was excellent. However, if the cationic polymer compound exceeds 50 parts by weight, the dispersion of the cationic polymer compound with respect to PVA may be poor, and particle-like irregularities may occur in the ink receiving layer of the resulting inkjet recording material. Attention should be paid to the distributed state.
[0013]
In addition to PVA and a cationic polymer compound, the resin composition for an inkjet recording material of the present invention can further contain a cationic activator or a nonionic activator. In the present invention, the content of the cationic activator or nonionic activator in the resin is preferably in the range of 1 wt% to 10 wt%.
Examples of the cationic active agent preferably used in the present invention include polyethyleneimine, quaternary ammonium chloride, quaternary ammonium sulfate and the like. Nonionic active agents preferably used in the present invention include polyoxyethylene alkylamine. And glycerin fatty acid ester.
[0014]
In the present invention, the PVA used for forming the ink receiving layer is a cold water soluble type PVA, preferably having a saponification degree of about 20 to 90%, and there is a difference between the decomposition temperature and the melting point (molding temperature). It is preferable that it is 20 degreeC or more.
In order to set the temperature difference between the decomposition temperature and the melting point to 20 ° C. or more, for example, the viscosity average polymerization degree of PVA is adjusted to 200 to 1000, or a copolymer of PVA and an ethylenic monomer is formed. The temperature difference can be increased to 20 ° C. or more by adding a plasticizer to PVA. When the temperature difference is set by forming a copolymer of PVA and an ethylenic monomer, for example, N-vinylpyrrolidone may be polymerized to about 10 mol%. When the temperature difference is set by adding a plasticizer, it is preferable to add about 15% by weight of glycerin, ethylene glycol or the like. In this way, the melting point of PVA can be 180 ° C. or lower, and therefore the temperature difference between the decomposition temperature and the melting point can be 20 ° C. or higher.
[0015]
Furthermore, the PVA used in the present invention has a weight average molecular weight (Mw) and a number average molecular weight (Mn) in order to improve necking (the film or sheet extruded from the extruder is shrunk in the transverse direction). The ratio (Mw / Mn) of 2.8 is preferably 2.8 or more.
[0016]
The resin composition of the present invention can contain a plasticizer or the like in order to improve the texture of the material such as the touch and softness of the ink jet recording material. Examples of the plasticizer preferably used in the present invention include polyethylene glycol (PEG). A filler can also be included to prevent blocking. Examples of the filler preferably used in the present invention include inorganic fillers such as talc.
[0017]
In order to form an ink receiving layer of an ink jet recording material using the resin composition of the present invention, after blending the resin, it is mixed using a twin screw extruder, preferably using a same direction twin screw extruder. Therefore, it is preferable to pelletize. The pelletization is preferably performed at a temperature of about 160 ° C.
Using the ink jet recording material of the present invention, image recording can be performed by a normal ink jet method, and a good image can be obtained.
[0018]
【Example】
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
Example 1
65 mol% of the ethylene structural unit represented by the general formula (1), 5 mol% of the acrylate structural unit represented by the general formula (2), and 30 mol of the acrylamide structural unit represented by the general formula (3) % Cationic polymer compound was prepared. However, in the cationic polymer compound, R ^{1 of the} acrylate structural unit represented by the general formula (2) is C ₂ H ₅ and R ^{2 of the} acrylamide structural unit represented by the general formula (3) is an ethylene group. , R ³ , R ⁴ and R ⁵ are each a methyl group, and X ⁻ is a cationic polymer compound of C ₂ H ₅ OSO ₃ ^— . The weight average molecular weight of the cationic polymer compound was 23,000. The molar fraction of each structural unit in the cationic polymer compound was determined by NMR measurement.
[0019]
Next, 70% by weight of PVA (trade name “CP-1000”, manufactured by Kuraray Co., Ltd.) and 30% by weight of the prepared cationic polymer compound were put into a twin screw extruder and mixed at a temperature of 160 ° C. Then, it was pelletized, and then melt-extruded at 190 ° C. using a twin-screw extruder to form a film having a thickness of 40 μm. Thereafter, the obtained film and a polyethylene terephthalate (PET) film having a thickness of 100 μm were laminated and laminated at a temperature of 190 ° C. to obtain an ink jet recording material of the present invention.
[0020]
Example 2
An ink jet recording material was prepared in the same manner as in Example 1 except that the ratio of PVA and cationic polymer compound charged into the twin screw extruder was changed to 50% by weight / 50% by weight.
[0021]
Example 3
An ink jet recording material was prepared in the same manner as in Example 1, except that the ratio of PVA and the cationic polymer compound charged into the twin-screw extruder was changed to 95% by weight / 5% by weight.
[0022]
Comparative Example 1
PVA (trade name “CP-1000”, manufactured by Kuraray Co., Ltd.) was melt-extruded with an extruder at 190 ° C. to produce a film having a thickness of 40 μm. Next, the obtained film and a polyethylene terephthalate (PET) film having a thickness of 100 μm were laminated at a temperature of 190 ° C. to obtain a comparative inkjet recording material.
[0023]
The ink jet recording materials of Examples 1 to 3 and Comparative Example 1 thus obtained were evaluated for humidity resistance such as printing quality (image quality) and ink bleeding according to the following evaluation method.
Evaluation Method 1) Evaluation of Print Output Quality Each of the inkjet recording materials (samples) of Example 1 and Comparative Example 1 was independently manufactured using a product name “Design Jet 350C” manufactured by Hewlett-Packard Company. Printed. The printed print pattern was observed with the naked eye to evaluate the print quality. However, the evaluation criteria are as follows.
Evaluation criteria:
A Excellent B Level “A” is not reached, but is within the practical level C Inferior
2) Evaluation of moisture resistance The ink jet recording material (sample) used in the evaluation of the print output quality is placed in a constant temperature and humidity chamber set at a temperature of 40 ° C. and a relative humidity of 90% RH and left for 24 hours. Evaluation was made on the blur. However, the blur of the line is indicated by the blur rate of the line according to the following formula. When the bleeding rate exceeds 110%, it becomes impractical.
[Expression 1]

However, after the test means that the sample is placed in a constant temperature and humidity chamber and left for 24 hours, and before the test means before the sample is put in a constant temperature and humidity chamber.
The obtained results are shown in Table 1.
[0025]
As is apparent from the results in Table 1, the recording material formed using the resin composition containing the specific cationic polymer compound according to the present invention has excellent print quality and the ink bleeding state. It was good and excellent in moisture resistance.
In particular, in Example 1 in which the weight ratio of PVA to the cationic polymer compound was in the range of 60/40 to 85/15, excellent results were obtained in both the print quality evaluation and the line blurring rate evaluation. In addition, the decomposition temperature of the brand name “CP-1000” of PVA used was 200 ° C., the melting point was 174 ° C., and the temperature difference was 26 ° C. However, the decomposition (starting) temperature was the starting temperature measured according to JIS-K-7120 as the decomposition temperature, and the melting point was the value measured according to JIS-K-0064.
In addition, generation | occurrence | production of the spot was not seen in the obtained ink receiving layer.
[0026]
Example 4
30 parts of polyvinyl acetate having a polymerization degree of 300 and Mw / Mn = 2.7 and 20 parts of polyvinyl acetate having a polymerization degree of 1700 and Mw / Mn = 2.7 were mixed with a methanol solution, After saponifying 60 mol% of the vinyl acetate part, it was dried to produce PVA (I) having a polymerization degree of 600 and Mw / Mn = 3.6. The temperature difference between the decomposition temperature and the melting point of the produced PVA (I) was 27 ° C.
[0027]
An ink jet recording material was prepared in the same manner as in Example 1, except that PVA (I) produced in place of the trade name “CP-1000” was used as PVA. However, PVA (I) and a cationic polymer compound were put into a twin-screw extruder, melt extrusion was performed, and extrusion at the time of producing a film having a thickness of 40 μm was good.
[0028]
Example 5
After saponifying 82 mol% of the vinyl acetate portion under an alkali catalyst into polyvinyl acetate copolymerized with 4 mol% of N-vinylpyrrolidone, it was dried and PVA having a polymerization degree of 500, Mw / Mn = 2.7 ( II) was prepared. In addition, polyvinyl acetate copolymerized with 4 mol% of N-vinylpyrrolidone was saponified with vinyl acetate in the presence of an alkali catalyst and then dried to obtain PVA (III) having a polymerization degree of 1700 and Mw / Mn = 2.7. Was prepared. 100 parts of PVA (II) and 20 parts of PVA (III) were mixed and polymerized to produce PVA (IV) having a polymerization degree of 940, Mw / Mn = 3.1, and a saponification degree of 83 mol%. The temperature difference between the decomposition temperature and the melting point of the produced PVA (IV) was 24 ° C.
[0029]
An ink jet recording material was produced in the same manner as in Example 1 except that PVA (IV) produced in place of the trade name “CP-1000” was used as PVA. However, PVA (IV) and a cationic polymer compound were charged into a twin-screw extruder and melt extrusion was performed, and the extrusion when producing a film having a thickness of 40 μm was good.
[0030]
The inkjet recording materials obtained in Example 4 and Example 5 were subjected to “evaluation of print output quality” and “evaluation of moisture resistance” in the same manner as in Example 1. The results are shown in Table 1. As is apparent from Table 1, both “evaluation of print quality” were evaluations of level “A”, and “line bleeding rate” was 100%, indicating good moisture resistance.
[0031]
[Table 1]

[0032]
【The invention's effect】
As described above in detail, the ink jet recording material prepared using the resin for ink jet recording material of the present invention has excellent printing quality and high temperature and high humidity because the cationic substance is dispersed in the ink receiving layer. Even when stored, the ink bleed state was good and the moisture resistance was excellent.

Claims (5)

Containing a polyvinyl alcohol and a cationic polymer compound extrusion grade jet recording blending ratio of the said polyvinyl alcohol and the cationic polymer compound is characterized in that it is in the range of 50 / 50-95 / 5 Resin composition for materials. In the cationic polymer compound, an ethylene structural unit represented by the following general formula (1) is 65 mol% to 99 mol%, an acrylate structural unit represented by the following general formula (2) is 15 mol% or less, and A linear cationic polymer compound having an irregularly arranged weight average molecular weight of 1,000 to 50,000, wherein the acrylamide structural unit represented by the general formula (3) is 1 mol% to 35 mol%. The resin composition for inkjet recording materials according to claim 1.

Wherein R ² represents an alkylene group having 2 to 8 carbon atoms, R ³ represents an alkyl group having 1 to 4 carbon atoms, and R ⁴ and R ⁵ are each independently an alkyl group having 1 to 12 carbon atoms. represents an alicyclic alkyl group having 1 to 12 arylalkyl group or a carbon number of 1 to 12 carbon atoms, X ^- is a halogen _ion, CH 3 OSO ₃ ^- represents a) ^- or _C 2 _H 5 OSO ₃ The resin composition for an inkjet recording material according to claim 1 or 2 , wherein a temperature difference between a decomposition temperature and a melting point of the polyvinyl alcohol is 20 ° C or more. The resin composition for an ink jet recording material according to any one of claims 1 to 3 , wherein a weight ratio of the polyvinyl alcohol to the cationic polymer compound is in a range of 60/40 to 85/15. . An inkjet recording material having an ink-receiving layer laminated by melt extrusion onto the substrate, the ink-receiving layer is formed by using the ink jet recording material for a resin composition according to any one of claims 1 to 4 An ink jet recording material.